Asymmetric diisocyanate monomers in urethane polymers and oligomers to reduce crystallinity

ABSTRACT

Compositions comprising a reaction product of a) an asymmetrical, saturated polyisocyanate that is non-cyclic, non-aromatic, and has at least 3 carbon atoms in the polyisocyanate per isocyanate group, b) a material that is at least one of i) a primary carbamate material having at least one functional group reactive with an isocyanate and at least one primary carbamate group or a group convertible to a primary carbamate group and ii) a reaction product of the primary carbamate material and an extending agent, and c) optionally, a chain extension agent that has at least difunctional reactivity with an isocyanate. Also, methods of making these compositions.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a non-provisional application of U.S. SerialNo. 60/341,470 filed on Dec. 17, 2001, which is incorporated herein byreference.

FIELD OF THE INVENTION

[0002] The present invention relates to urethane polymers and oligomers.

BACKGROUND OF THE INVENTION

[0003] Curable, or thermosettable, coating compositions are widely usedin the coatings art, particularly for topcoats in the automotive andindustrial coatings industry. Color-plus-clear composite coatings areparticularly useful as topcoats for which exceptional gloss, depth ofcolor, distinctness of image, or special metallic effects are desired.The automotive industry has made extensive use of these coatings forautomotive body panels.

[0004] Single-layer topcoats and the clearcoats of color-plus-clearcomposite coatings, however, require an extremely high degree of clarityand gloss to achieve the desired visual effect. Such coatings alsorequire a low degree of visual aberrations at the surface of the coatingin order to achieve the desired visual effect such as high distinctnessof image (DOI). As such, these coatings are especially susceptible to aphenomenon known as environmental etch. Environmental etch manifestsitself as spots or marks on or in the finish of the coating that oftencannot be rubbed out. It is often difficult to predict the degree ofresistance to environmental etch that a high gloss topcoat orcolor-plus-clear composite coating will exhibit. Many coatingcompositions known for their durability and/or weatherability when usedin exterior paints, such as known high-solids enamels, do not providethe desired level of resistance to environmental etch when used in highgloss coatings such as the clearcoat of a color-plus-clear compositecoating. Curable coating compositions based on curable components havingcarbamate or urea functionality have been proposed have been describedin the art to provide etch-resistant coatings, e.g., U.S. Pat. Nos.5,356,669; 5,373,069; 5,854,385; and 6,245,855.

[0005] Various compositions have been proposed to meet the aboverequirements for use as the topcoat coating or as the clearcoat of acolor-plus-clear composite coating, including polyurethanes, acid-epoxysystems and the like. However, many prior art systems suffer fromdisadvantages such as coatability problems, marginal compatibility withthe pigmented basecoat, solubility problems, and marginal appearance.Moreover, while one-pack compositions are preferred to two-packcompositions (in which the reactive component must be separated beforeapplication to prevent premature reaction), very few one-pack coatingcompositions have been found that provide satisfactory resistance toenvironmental etch, especially in the demanding environment ofautomotive coatings.

[0006] In addition, it is desirable to provide coatings with a goodcombination of properties such as durability, hardness, flexibility, andresistance to scratching, marring, solvents, and acids. It is alsodesirable to reduce the amount of solvent required in coatingcompositions in order to reduce the volatile organic content (VOC),which is better for the environment. In addition to etch resistance,scratch and mar resistance is a desired property for a coating. Scratchand marring resistance is the ability of a coating to resist damagecaused by abrasion of the coating.

[0007] Curable coating compositions utilizing carbamate-functionalresins are described, for example, in U.S. Pat. Nos. 6,245,855;6,160,058; 6,165,618; 6,144,444; 6,084,038; 6,080,825; 6,040,062;5,994,479; 5,888,655; 5,872,195; 5,866,259; 5,854,385; 5,852,136;5,827,930; 5,792,810; 5,777,048; 5,770,650; 5,766,769; 5,760,127;5,756,213; 5,744,550; 5,726,274; 5,726,246; 5,726,244; 5,723,552;5,693,724; 5,693,723; 5,659,003; 5,639,828; 5,532,061; 5,512,639;5,508,379; 5,474,811; 5,451,656; 5,373,069; 5,356,669; 5,336,566; and5,300,328 each of which is incorporated herein by reference, and U.S.application Ser. Nos. 08/719,670, filed Sep. 25, 1996 (EP832950),08/166,277, filed Dec. 13, 1993, 08/339,999, filed Nov. 15, 1994,09/211,598, filed Dec. 14, 1998 (WO0036028), 07/965,509, filed Oct. 23,1992 (CA2108990), and 08/540,276 and 08/698,525 both filed Oct. 6, 1995(CA2187222) each of which is incorporated herein by reference. Thesecoating compositions can provide significant etch advantages over othercoating compositions, such as hydroxy-functional acrylic/melaminecoating compositions. It may often be desirable, however, to providestill further improvements in the above-described coating properties.

[0008] When a symmetrical isocyanate is included in a urethane reactionproduct, the resulting urethane tends to be crystalline.

SUMMARY OF THE INVENTION

[0009] The present invention relates to a composition comprising areaction product of a) an asymmetrical, saturated polyisocyanate that isnon-cyclic, non-aromatic, and has at least 3 carbon atoms in thepolyisocyanate per isocyanate group, b) a material that is at least oneof i) a primary carbamate material having at least one functional groupreactive with an isocyanate and at least one primary carbamate group ora group convertible to a primary carbamate group and ii) a reactionproduct of the primary carbamate material and an extending agent, and c)optionally, a chain extension agent that has at least difunctionalreactivity with an isocyanate.

[0010] Also, a the present invention relates to a method comprisingreacting a) an asymmetrical, saturated polyisocyanate that isnon-cyclic, non-aromatic, and has at least 3 carbon atoms in thepolyisocyanate per isocyanate group, a material that is at least one ofi) a primary carbamate material having at least one functional groupreactive with an isocyanate and at least one primary carbamate group ora group convertible to a primary carbamate group and ii) a reactionproduct of the primary carbamate material and an extending agent, and c)optionally, a chain extension agent that has at least difunctionalreactivity with an isocyanate.

DETAILED DESCRIPTION

[0011] As used throughout, ranges are used as a shorthand for describingeach and every value that is within the range. Any value within therange can be selected as the terminus of the range.

[0012] In one embodiment, the present invention is a compositioncomprising a reaction product of a) an asymmetrical, saturatedpolyisocyanate that is non-cyclic, non-aromatic, and has at least 3carbon atoms in the polyisocyanate per isocyanate group, and b) amaterial that is at least one of a primary carbamate material having atleast one functional group reactive with an isocyanate and at least oneprimary carbamate group or a group convertible to a primary carbamategroup and ii) a reaction product of the primary carbamate material andan extending agent. As used herein, the term reaction material refers tothe materials that react to form the reaction product.

[0013] The present invention provides compositions that include anasymmetrical, saturated polyisocyanate that is non-cyclic, non-aromatic,and has at least 3 carbon atoms in the polyisocyanate per isocyanategroup in their molecules. By poly it is meant that there are at leasttwo isocyanate groups in the molecule. Preferably, the asymmetrical,saturated polyisocyanate is a diisocyanate. By non-cyclic andnon-aromatic it is meant that no portion of the polyisocyanate is cyclicor aromatic. Preferably, the asymmetrical, saturated polyisocyanate is anon-crystalline aliphatic. Because of its commercial availability, apreferred asymmetrical, saturated polyisocyanate istrimethylhexamethylene diisocyanate. Trimethylhexamethylene diisocyanate(TMDI) generally has at least the following two isomers in commerciallyavailable product: 1,6-diisocyanto-2,2,4-trimethyl hexane and1,6-diisocyanto-2,4,4-trimethyl hexane. As used throughout thisspecification, reference to trimethylhexamethylene diisocyanate is tothe commercial blend of isomers. Another preferred polyisocyanate is1,8-diisocyanto-4(isocyantomethyl)octane. The polyisocyanate can also beprovided as a dimer, trimer, homopolymer, or as a polyurethaneprepolymer of the polyisocyanate.

[0014] By asymmetrical it is meant that the polyisocyanate does not havesymmetry in its structure. Symmetry is defined in the followingapplications, U.S. Ser. Nos. 09/211,577; 09/211,578; 09/211,579; and09/211,598 all filed on Dec. 14, 1998, and all are incorporated hereinby reference. Briefly, symmetry operations are geometrically definedways of exchanging equivalent parts of a molecule. However, suchoperations are symmetry operations if, and only if, the appearance ofthe molecule is exactly the same relative to the pre- and post-symmetryoperation view. Thus, the term “symmetrical” as used herein refers to amolecule having an appearance that appears identical relative to thepre- and post-symmetry operation views. Put another way, “[a] moleculepossesses a symmetry element if the application of the operationgenerated by the element leaves the molecule in an indistinguishablestate.” Molecular Symmetry and Group Theory, Alan Vincent, Wiley & Sons,NY, 1977, reprinted 1981, page 21, incorporated herein by reference.

[0015] Additionally, when there are less than 3 carbon atoms in thepolyisocyanate per isocyanate group, products that contain thesepolyisocyanates are generally more crystalline. Note, when counting thecarbon atoms in a polyisocyanate, the carbon atom that is in theisocyanate group is part of the isocyanate group and is not counted as acarbon in the polyisocyanate.

[0016] Without being limited to theory, it is theorized thatpolyisocyanates that have freedom of motion in their backbones increasethe flexibility of products that contain them. Generally,polyisocyanates that contain cyclics, aromatics, or are ethylenicallyunsaturated, such as alkenes or alkynes, do not provide freedom ofmovement that is preferred to obtain maximum levels of flexibility.

[0017] The primary carbamate material can be any primary carbamatematerial that has at least one functional group that is reactive with anisocyanate and at least one primary carbamate group or a group that isconvertible to a primary carbamate group. The functional group that isreactive with an isocyanate group includes, but is not limited to, ahydroxyl group, an amine group, and a thiol group. A preferredfunctional group is a hydroxyl group. A preferred primary carbamatematerial has a primary carbamate group and a hydroxy group, which isseparated from the primary carbamate group by at least two carbon atoms.A preferred primary carbamate material of this type is a hydroxyalkylcarbamate. A preferred hydroxyalkyl carbamate is represented by thefollowing structure:

[0018] wherein R₁, R₂, R₃, R₄, R₅, and R₆ are each independently H orC₁-C₆ alkyl, and n is 0 or a positive integer. Preferably, R₁, R₂, R₃,R₄, R₅, and R₆ are each independently H or C₁-C₄ alkyl. Examples ofprimary carbamate materials include, but are not limited to, hydroxyethyl carbamate, hydroxy propyl carbamate, and hydroxy butyl carbamate.A preferred hydroxyalkyl carbamate is hydroxypropyl carbamate, which isat least one of 2-hydroxy propyl-1-carbamate, 1-hydroxypropyl-2-carbamate, and 3-hydroxypropyl carbamate. Hydroxy butylcarbamate includes, but is not limited to, 1-hydroxy butyl-2-carbamate,2-hydroxy butyl carbamate, and 4-hydroxybutyl carbamate.

[0019] The group convertible or capable of converting to a primarycarbamate group can form a primary carbamate after the reaction of theprimary carbamate material with the asymmetrical, saturatedpolyisocyanate is completed. These types of primary carbamate materialsinclude, but are not limited to, hydroxy-containing cyclic carbonatecompounds, such as glycerine carbonate, which are convertible to primarycarbamate by reaction with ammonia (e.g., the reaction product ofglycidol and CO₂), monoglycidyl ethers (e.g., glycidyl propyl etherconvertible to primary carbamate by reaction with CO₂ and then ammonia),allyl alcohols where the alcohol group is reactive with NCO and thedouble bond can be converted to primary carbamate by reaction withperoxide, and vinyl esters where the ester group is reactive with NCOand the vinyl group can be converted to primary carbamate with reactionwith peroxide, then CO₂, and then ammonia. Also suitable as the primarycarbamate material are compounds having a primary carbamate group aswell as a group that can be converted into a primary carbamate. Theprimary carbamate group can then react with the isocyanate group to forman allophanate. The primary carbamate-convertible group can then beconverted into a primary carbamate. An example of such a compound isallyl carbamate. In another example, the isocyanate can be reacted witha diol or amino alcohol to form a urethane or urea compound withterminal or pendant hydroxy groups. The terminal or pendant hydroxygroups can then be transformed into primary carbamate groups using knowntechniques, such as the reaction with phosgene then ammonia, or bytranscarbamation with an alkyl or ether carbamate.

[0020] Preferably, the primary carbamate material is asymmetrical and/ora mixture of isomers. As a non-limiting example of a mixture of isomers,the primary carbamate material can be a mixture of at least two of2-hydroxy propyl-1-carbamate, 1-hydroxy propyl-2-carbamate, and3-hydroxypropyl carbamate.

[0021] The material can also be provided as a reaction product of theprimary carbamate material and an extending agent to form a prepolymer.The extending agent is any material that is reactive with the at leastone functional group that is reactive with an isocyanate in the primarycarbamate material and will polymerize in a head to tail arrangementwith monomer units. When the functional group is hydroxy, the chainextension agent includes, but is not limited to, lactones and hydroxycarboxylic acids. Preferred lactones are ε-caprolactone and butyllactone. A preferred carboxylic acid is 12-hydroxydodecanoic acid. Theextending agent can also be an oxiran-functional material, such asalkylene oxides. Preferred oxiran functional materials include, but arenot limited to, ethylene oxide and propylene oxide. Optionally, theextending agent is asymmetrical. In the prepolymer, there can be anynumber of extending agents connected to each other per carbamate. In thefollowing ranges, the numbers listed are based on an average of allmolecules in a given sample. Preferably there are from 1 to about 20extending agents connected to each other per carbamate. Preferably, inthe prepolymer, there are from I to about 6 extending agents connectedto each other per primary carbamate material. More preferably, there are1 to about 3 extending agents connected to each other per primarycarbamate material. More preferably, there are about 2 extending agentsconnected to each other per primary carbamate material. More preferably,there are about 1.5 extending agents connected to each other per primarycarbamate material. Even more preferably, there is one extending agentper primary carbamate material. A preferred prepolymer has the structureHAC-(extending agent)_(n)-OH, wherein HAC is hydroxy alkyl carbamate ora group that can be converted to a primary carbamate, and n is a numberthat is at least 1.

[0022] The material can also be a blend of the primary carbamatematerial with the prepolymer. In a preferred embodiment, the primarycarbamate material is about 10% to about 90% of the blend based on theequivalents of carbamate groups. More preferably, the primary carbamateis about 40-90% of the blend based on the equivalents of the carbamategroups. Even more preferably, the primary carbamate material is about60% to about 90% of the blend based on the equivalents of thecarbam-tate group.

[0023] Additionally, a chain extension agent having at leastdifunctional reactivity with an isocyanate has at least two reactivegroups that react with isocyanate groups can be reacted with the otherreaction materials. Preferably, there are 2 reactive groups per chainextension agent. Preferably, the reactive groups are hydroxyl, amine,thiol, and combinations thereof. More preferably, the reactive groupsare hydroxyl. Optionally, the material can have a pendant alkyl chain.The pendant alkyl chain is the portion of the molecule that is oppositeof the terminal reactive group and at a location beyond where thesecondary reactive group attaches to the molecule. Also, the chainextension agent may contain heteroatoms, such as O, N, and Si.Optionally, the chain extension agent can be asymmetrical.

[0024] The reactive groups of the chain extension agent are placed onthe molecular structure such that each reactive group can have the samereactivity or a different reactivity with respect to the other reactivegroups. When the groups have different reactivity, at least two of thegroups have a different reactivity with respect to the other reactivegroups. When there are more than two reactive groups, some of the groupscan have the same reactivity with respect to each other and a differentreactivity with respect to other groups. When the reactivity is thesame, the carbon atoms are all primary, all secondary, all tertiary, orare all substituted to the same degree with the same substituents. Whenthe reactivity is different, the reactive groups are attached to carbonatoms that are not the same with respect to each other. When thereactive groups are amine groups, in addition to the attachment of theamine group to the different carbon atoms, a difference in reactivitycan be obtained by changing the substituents on the amine group itself

[0025] Examples of the chain extension agent with at least twofunctional groups that have different reactivity with respect to eachother include, but are not limited to, 2-ethyl-1,3 hexanediol,2-methyl-2,4-pentane diol, 2,2,4-trimethyl-1,3-pentanediol,2,4-diethyl-1,5-octanediol, 1-hydroxymethyl cyclohexan-4-ol,1-amino-hexan-6-ol, 2-ethyl-3-N-methyl-1,3-hexanediamine, isomers ofthese materials, and mixtures thereof. Examples of the chain extensionagent with at least two functional groups that have the same reactivitywith respect to each other include, but are not limited to, 1,6-hexanediol and 1,10-decane diol. Examples of the chain extension agent thatare asymmetrical are 2-methyl-1,6-hexane diol and 3-methyl-1,10-decanediol.

[0026] Preferably, the reaction product has a glass transitiontemperature, T_(g), that is less than or equal to about 30° C. One wayto provide this T_(g) is with a low T_(g) polyisocyanate, which can bedetermined by reacting the polyisocyanate with methanol to form aproduct and then measuring the T_(g) of the product.

[0027] Without being limited to theory, it is theorized that the lack ofsymmetry in the isocyanate, and optionally in the chain extension agent,the primary carbamate material, and/or the extending agent, lowers thecrystallinity in the reaction product. This, combined with the low T_(g)of the reaction product, lowers the amount of organic solvent that isneeded to form a coating composition. The lower amount of solventprovides for a lower volatile organic chemical (VOC) content for acoating composition. The VOC that can be obtained by the compositions ofthe present invention are less than or equal to about 432.4 g/l (3.6lb./gal.), preferably less than or equal to 192.2 g/l (1.6 lb./gal.),and more preferably less than or equal to 48 g/l (0.4 lb./gal.).

[0028] It is also theorized that reaction products that contain symmetrycan precipitate out of organic solutions. Additionally, the low T_(g) ofthe reaction product provides flexibility to the reaction product. LowT_(g) of the reaction product can also help lower the VOC and mayimprove scratch and mar.

[0029] In a preferred embodiment, the reaction product is soluble inorganic solvents. Examples of organic solvents include, but are notlimited to, aliphatic solvents, aromatic solvents, ketone solvents,alcohols, and ester solvents.

[0030] In a preferred embodiment, the chain extension agent has twohydroxyl groups that have different reactivity.

[0031] A preferred reaction product, when the chain extension agent isnot included, can be represented by the following structure:(material)-(asymmetrical, saturated polyisocyanate)-(material). Apreferred reaction product, when the chain extension agent is included,can be represented by the following structure: (material)-(asymmetrical,saturated polyisocyanate)-(chain extension agent-asymmetrical, saturatedpolyisocyanate),-(material), wherein m is any number that is at least 1and is based on an average of all reaction products, and material isdefined above. In this preferred reaction product, the carbamate groupsof the material are the terminal ends of the reaction product.

[0032] In a preferred embodiment, the material is provided as a blend ofthe primary carbamate material and the reaction product of the primarycarbamate material with the extending agent. Preferably in thispreferred embodiment, the ratio of urethane structures to esterstructures in the reaction product is at least 2:1. More preferably, theratio of urethane structures to ester structures is at least 4:1, with4:1 being preferred.

[0033] In a preferred embodiment, the reaction product has a numberaverage molecular weight of about 464 to about 4000. More preferably,the reaction product has a number average molecular weight of less thanabout 1500.

[0034] The present invention also provides a method for making areaction product, which comprises reacting a) the asymmetrical,saturated polyisocyanate, the material that is at least one of i) theprimary carbamate material having at least one functional group reactivewith an isocyanate and at least one primary carbamate group or a groupconvertible to a primary carbamate group and ii) the reaction product ofthe primary carbamate material and an extending agent, and c)optionally, the chain extension agent that has at least difunctionalreactivity with an isocyanate When the chain extension agent is includedin the reaction, the reacting is one of: a) reacting the polyisocyanate,the chain extension agent, and the material together in one reaction, b)reacting the polyisocyanate with the chain extension agent to form areaction product A, and then reacting reaction product A with thematerial, and c) reacting the material with the polyisocyanate to form areaction product B, and then reacting reaction product B with the chainextension agent.

[0035] The reaction of the reaction materials can be started with acatalyst. The catalyst can be any catalyst in any amount thatfacilitates reaction of the reaction materials. Examples of suchcatalysts include, but are not limited to, stannous octoate, octanoicacid, dibutyltin dilaurate, dibutyl tin oxide, and weak acids.

[0036] The reaction can optionally take place in the presence of asolvent. The solvent can be any solvent in any amount that solubilizesthe reaction materials. Examples of the solvent include, but are notlimited to, organic solvents, polar organic solvents, polar aliphaticsolvents, polar aromatic solvents, ketones, esters, acetates, aproticamides, aprotic sulfoxides, aprotic amines, toluene, xylene, methylethyl ketone, methyl isobutyl ketone, m-amyl acetate, ethylene glycolbutyl ether acetate, propylene glycol monomethyl ether acetate,n-methylpyrrolidone, blends of aromatic hydrocarbons, and mixturesthereof.

[0037] In a preferred reaction, based on the combined weight of thereaction materials, the amount of asymmetrical, saturated polyisocyanateranges from about 20 to about 60% by weight, and the amount of materialhaving at least one functional group reactive with an isocyanate and atleast one primary carbamate group or a group convertible to a primarycarbamate group ranges from about 30 to about 70% by weight.

[0038] Generally, the reaction temperature for this reaction iscontrolled from about 0° C. to about 110° C., preferably from about 20°C. to about 90° C. Generally, the amount of initiator ranges from about0.01 to about 0.1% by weight of the isocyanate. The amount of solventgenerally ranges in an amount such that the % non-volatiles ranges fromabout 10 to about 90%. Generally, the reaction is generally taken togreater than 90% completion as measured by NCO content.

[0039] Another non-limiting example of a product of the presentinvention comprises a molecule of the following structure:

[0040] wherein R₁, R₂, R₆, and R₇ are defined above.

[0041] The composition of the present invention can further includeadditional polymers. Examples of the additional polymer include, but arenot limited to, an acrylic, a vinyl, a polyurethane, a polycarbonate, apolyester, an alkyd, and a polysiloxane.

[0042] The compositions of the present invention can be included incoating compositions. The coating composition can include, but is notlimited to, materials described below. The coating composition can beused as any layer in a coating, which includes, but is not limited to,electrodeposition coating, primer, base coat, top coat, clearcoat, andlaminate.

[0043] A solvent may optionally be utilized in the coating compositionused in the practice of the present invention. Although the compositionused according to the present invention may be utilized, for example, inthe form of substantially solid powder, or a dispersion, it is oftendesirable that the composition is in a substantially liquid state, whichcan be accomplished with the use of a solvent. This solvent should actas a solvent with respect to the components of the composition. Ingeneral, the solvent can be any organic solvent and/or water. In onepreferred embodiment, the solvent is a polar organic solvent. Morepreferably, the solvent is selected from polar aliphatic solvents orpolar aromatic solvents. Still more preferably, the solvent is a ketone,ester, acetate, aprotic amide, aprotic sulfoxide, aprotic amine, or acombination of any of these.

[0044] Examples of useful solvents include, but are not limited to,methyl ethyl ketone, methyl isobutyl ketone, m-amyl acetate, ethyleneglycol butyl ether-acetate, propylene glycol monomethyl ether acetate,xylene, N-methylpyrrolidone, blends of aromatic hydrocarbons, andmixtures of these. In another preferred embodiment, the solvent is wateror a mixture of water with small amounts of co-solvents.

[0045] The coating composition used in the practice of the invention mayinclude a catalyst to enhance the cure reaction. For example, whenaminoplast compounds, especially monomeric melamines, are used as acuring agent, a strong acid catalyst may be utilized to enhance the curereaction. Such catalysts are well-known in the art and include, withoutlimitation, p-toluenesulfonic acid, dinonylnaphthalene disulfonic acid,dodecylbenzenesulfonic acid, phenyl acid phosphate, monobutyl maleate,butyl phosphate, and, hydroxy phosphate ester. Strong acid catalysts areoften blocked, e.g. with an amine. Other catalysts that may be useful inthe composition of the invention include Lewis acids, zinc salts, andtin salts.

[0046] In a preferred embodiment of the invention, the solvent ispresent in the coating composition in an amount of from about 0.01weight percent to about 99 weight percent, preferably from about 10weight percent to about 60 weight percent, and more preferably fromabout 30 weight percent to about 50 weight percent.

[0047] Coating compositions can be applied on an article/substrate byany of a number of techniques well-known in the art. These include, forexample, spray coating, dip coating, roll coating, curtain coating, andthe like. For automotive body panels, spray coating is preferred.

[0048] Additional agents, for example crosslinkers, surfactants,fillers, stabilizers, wetting agents, dispersing agents, adhesionpromoters, UV absorbers, hindered amine light stabilizers, etc. may beincorporated into the coating composition. A preferred crosslinker is anaminoplast. Preferably, the aminoplast is based on melamine orbenzoquanamine. Preferred aminoplast resins are melamine formaldehyderesins (including monomeric or polymeric melamine resins and partiallyor fully alkylated melamine resins) or urea formaldehyde resins.

[0049] While such additives are well-known in the prior art, the amountused must be controlled to avoid adversely affecting the coatingcharacteristics.

[0050] The coating composition according to the invention is preferablyutilized in a high-gloss coating and/or as the clearcoat of a compositecolor-plus-clear coating. High-gloss coatings as used herein arecoatings having a 20° gloss (ASTM D523-89) or a DOI (ASTM E430-91) of atleast 80.

[0051] When the coating composition of the invention is used as ahigh-gloss pigmented paint coating, a coloring agent can be added to thecoating composition. Examples of the coloring agent include, but are notlimited to, any organic or inorganic compounds or colored materials,fillers, metallic or other inorganic flake materials such as mica oraluminum flake, and other materials of kind that the art normallyincludes in such coatings. Coloring agents and other insolubleparticulate compounds such as fillers are usually used in thecomposition in an amount of 1% to 100%, based on the total solid weightof binder components (i.e., a pigment-to-binder ratio of 0.1 to 1).

[0052] When the coating composition according to the invention is usedas the clearcoat of a composite color-plus-clear coating, the pigmentedbasecoat composition may be any of a number of types well-known in theart. Polymers known in the art to be useful in basecoat compositionsinclude acrylics, vinyls, polyurethanes, polycarbonates, polyesters,alkyds, and polysiloxanes. Preferred polymers include acrylics andpolyurethanes. In one preferred embodiment of the invention, thebasecoat composition also utilizes a carbamate-functional acrylicpolymer. Basecoat polymers may be thermoplastic, but are preferablycrosslinkable and comprise one or more type of crosslinkable functionalgroups. Such groups include, for example, hydroxy isocyanate, amine,epoxy, acrylate, vinyl, silane, and acetoacetate groups. These groupsmay be masked or blocked in such a way so that they are unblocked andavailable for the crosslinking reaction under the desired curingconditions, generally elevated temperatures. Useful crosslinkablefunctional groups include hydroxy, epoxy, acid, anhydride, silane, andacetoacetate groups.

[0053] Preferred crosslinkable functional groups include hydroxyfunctional groups and amino functional groups.

[0054] Basecoat polymers may be self-crosslinkable, or may require aseparate crosslinking agent that is reactive with the functional groupsof the polymer. When the polymer comprises hydroxy functional groups,for example, the crosslinking agent may be an aminoplast resin,isocyanate and blocked isocyanates (including isocyanurates), and acidor anhydride functional crosslinking agents.

[0055] The coating compositions described herein are preferablysubjected to conditions so as to cure the coating layers. Althoughvarious methods of curing may be used, heat-curing is preferred.Generally, heat curing is effected by exposing the coated article toelevated temperatures provided primarily by radiative heat sources.Curing temperatures will vary depending on the particular blockinggroups used in the cross-linking agents, however they generally rangefrom 90° C. to 180° C. The first compounds according to the presentinvention are preferably reactive even at relatively low curetemperatures. Thus, in a preferred embodiment, the cure temperature ispreferably from 115° C. to 1 50° C., and more preferably at temperaturesfrom 115° C. to 140° C. for a blocked acid catalyzed system. For anunblocked acid catalyzed system, the cure temperature is preferably from80° C. to 100° C. The curing time will vary depending on the particularcomponents used, and physical parameters such as the thickness of thelayers, however, typical curing times range from 15 to 60 minutes, andpreferably 15-25 minutes for blocked acid catalyzed systems and 10-20minutes for unblocked acid catalyzed systems.

[0056] Compositions of the present invention can provide coatings withimproved properties. The flex that can be obtained ranges from about 8to about 10 as measured by test method General Motors GM9503P. Also, theetch that can be obtained ranges from about 2 to about 8 as measured bytest method General Motors World Specification GM W-3005 paragraph 5.15,and more preferably ranges from about 2 to about 6.

SPECIFIC EMBODIMENTS OF THE INVENTION

[0057] The invention is further described in the following examples. Theexamples are merely illustrative and do not in any way limit the scopeof the invention as described and claimed. All parts are parts by weightunless otherwise noted.

EXAMPLE 1

[0058] A reactor equipped with an agitator, a thermocouple, and anitrogen gas inlet was charged with 340.1 g of hydroxypropyl carbamate,86.2 g of propylene glycol monomethyl ether acetate, and 0.35 g ofdibutyltin dilaurate and heated to 60° C. Stepwise in ⅛ amounts, 307.6 gof trimethylhexamethylene diisocyanate was added and allowed to react.Finally, 13.3 g of isobutanol and 200.7 g of propylene glycol monomethylether acetate were added.

EXAMPLE 2

[0059] A reactor equipped with an agitator, a thermocouple, and anitrogen gas inlet was charged with 194.6 g of hydroxypropyl carbamate,118.1 g 2-ethyl-1,3-hexane diol, 65.6 g of propylene glycol monomethylether acetate, and 0.34 g of dibutyltin dilaurate and heated to 60° C.Stepwise in ⅛ amounts, 350.3 g of trimethylhexamethylene diisocyanatewas added and allowed to react. Finally, 13.1 g of isobutanol and 268.8g of propylene glycol monomethyl ether acetate were added. Thecomposition had a non-volatile content of 66.5 with a viscosity of 76.5poise as measured on a BROOKFIELD™ cone and plate viscometer at 25° C.This composition had higher non-volatiles and was able to stay insolution as compared to Comparative Example 4.

COMPARATIVE EXAMPLE 3

[0060] A reactor equipped with an agitator, a thermocouple, and anitrogen gas inlet was charged with 839.4 g of hydroxypropyl carbamate,889.2 g of propylene glycol monomethyl ether acetate, 514.6 g of2-ethyl-1,3-hexane diol, and 1.25 g of dibutyltin dilaurate and heatedto 60° C. Stepwise, 150ml of 1,6-diisocyanto hexane, 125 ml of1,6-diisocyanto hexane, and the balance of 1244.4 g of 1,6-diisocyantohexane were added. Next, 197 g of propylene glycol monomethyl etheracetate, 53.9 g of isobutanol, and 342.7 g of isopropanol were added.The composition had a non-volatile content of 64.4%. The composition wascrystalline and would not stay in solution. Even with the addition ofadditional solvent, the reaction product would not stay in solution.

COMPARATIVE EXAMPLE 4

[0061] A reactor equipped with an agitator, a thermocouple, and anitrogen gas inlet was charged with 49.4 parts of methyl ethyl ketoneand was heated to reflux under an inert atmosphere to remove any water.The reactor was cooled to 50° C., and 21 parts of hexane diisocyanateand 0.0004 parts of dibutyl tin dilaurate were added. The reactionmixture was cooled to 40° C., and 28.2 parts of hydroxypropyl carbamatewere slowly added. During this addition, the reaction mixture wasallowed to exotherm to 75° C. The reaction was held at 75° C. Forty-fiveminutes into the hold, the product precipitated out of solution, forminga solid mass.

EXAMPLE 5

[0062] A reactor equipped with an agitator, a thermocouple, and anitrogen gas inlet was charged with 49.4 parts water free methyl ethylketone. Next, 23.7 parts of trimethylhexanediisocyanate (a mixture of2,2,4-trimethylhexanediisocyanate and 2,4,4-trimethylhexanediisocyanate)and 0.0004 parts of dibutyl tin dilaurate were added to the reactor at49° C. The reaction mixture was cooled to 39° C., and 25.5 parts ofhydroxypropyl carbamate were added. During the addition, the reactiontemperature increased to 73° C. Once the add was complete, the reactionwas heated to 75° C. and held. No precipitate formed after 2 hours and25 minutes at 75° C. After this time, 1.3 parts of isobutyl alcohol wereadded to remove any unreacted isocyanate, and the mixture was allowed tocool down. The reaction mixture was still in solution the next day.

[0063] It should be appreciated that the present invention is notlimited to the specific embodiments described above, but includesvariations, modifications and equivalent embodiments defined by thefollowing claims.

What is claimed is:
 1. A composition comprising a reaction product of a.an asymmetrical, saturated polyisocyanate that is non-cyclic,non-aromatic, and has at least 3 carbon atoms in the polyisocyanate perisocyanate group, b. a material that is at least one of i. a primarycarbamate material having at least one functional group reactive with anisocyanate and at least one primary carbamate group or a groupconvertible to a primary carbamate group, and ii. a reaction product ofthe primary carbamate material and an extending agent, and c.optionally, a chain extension agent that has at least difunctionalreactivity with an isocyanate.
 2. The composition of claim 1, whereinthe functional group reactive with an isocyanate on the primarycarbamate material is at least one of a hydroxyl group, an amine group,and a thiol group.
 3. The composition of claim 1, wherein the primarycarbamate material is at least one of a hydroxyalkyl carbamate, a ringopened glycerine carbonate, and an allyl alcohol reaction product. 4.The composition of claim 1, wherein the primary carbamate material isrepresented by the following structure:

wherein R₁, R₂, R₃, R₄, R₅, and R₆ are each independently H or C₁-C₆alkyl, and n is 0 or a positive integer.
 5. The composition of claim 1,wherein the primary carbamate material is at least one of hydroxy ethylcarbamate, hydroxy propyl carbamate, and hydroxy butyl carbamate.
 6. Thecomposition of claim 1, wherein the extending agent is at least one of alactone and a hydroxy carboxylic acid.
 7. The composition of claim 1,wherein the extending agent is ε-caprolactone.
 8. The composition ofclaim 1, wherein the material is a blend of the primary carbamatematerial and the reaction product of the primary carbamate material andthe extending agent.
 9. The composition of claim 8, wherein in theblend, the primary carbamate material is present in an amount from about10% to about 90% based on the equivalents of carbamate groups.
 10. Thecomposition of claim 1, wherein in the reaction product of the primarycarbamate material and the extending agent, there are from 1 to about 20extending agents connected to each other per primary carbamate materialbased on an average of all reaction product molecules.
 11. Thecomposition of claim 1, wherein in the reaction product of the primarycarbamate material and the extending agent, there are from 1 to about 3extending agents connected to each other per primary carbamate materialbased on an average of all reaction product molecules.
 12. Thecomposition of claim 1, wherein in the reaction product of the primarycarbamate material and the extending agent, there is 1 extending agentper primary carbamate material.
 13. The composition of claim 1, whereinthe asymmetrical, saturated polyisocyanate is a trimethylhexamethylenepolyisocyanate.
 14. The composition of claim 1, wherein theasymmetrical, saturated polyisocyanate is1,8-diisocyanto-4-(isocyantomethyl)octane.
 15. The composition of claim1, wherein the asymmetrical, saturated polyisocyanate is at least one ofa dimer of a polyisocyanate, a trimer of a polyisocyanate, a homopolymerof a polyisocyanate, and a polyurethane prepolymer of a polyisocyanate.16. The composition of claim 1, wherein the chain extension agent hastwo functional groups reactive with an isocyanate.
 17. The compositionof claim 1, wherein the functional group reactive with an isocyanate onthe chain extension agent is at least one of hydroxyl, amine, and thiol.18. The composition of claim 1, wherein the chain extension agent hastwo hydroxyl groups.
 19. The composition of claim 1, wherein the chainextension agent contains a heteroatom.
 20. The composition of claim 1,wherein the chain extension agent is selected from the group consistingof 2-ethyl-1,3 hexanediol; 2-methyl-2,4-pentane diol;2,2,4-trimethyl-1,3-pentanediol; 2,4-diethyl-1,5-octanediol;1-hydroxymethyl cyclohexan-4-ol; 1-amino-hexan-6-ol;2-ethyl-3N-methyl-1,3-hexane diamine; isomers of the precedingmaterials; 1,6-hexane diol; 1,10-decane diol; 2-methyl-1,6-hexane diol;3-methyl-1,10-decane diol, and mixtures thereof.
 21. The composition ofclaim 1, wherein the chain extension agent is asymmetrical.
 22. Thecomposition of claim 1, wherein the primary carbamate material isasymmetrical.
 23. The composition of claim 1, wherein the extendingagent is asymmetrical.
 24. The composition of claim 1, wherein theprimary carbamate material, the extending agent, and the chain extensionagent are each asymmetrical.
 25. The composition of claim 1, wherein theprimary carbamate material is a mixture of isomers.
 26. The compositionof claim 1, wherein the primary carbamate material is a mixture ofisomers and is asymmetrical.
 27. The composition of claim 1, wherein thereaction product is soluble in at least one of an aliphatic solvent,aromatic solvent, a ketone solvent, an alcohol, and an ester solvent.28. The composition of claim 1, wherein the reaction product has a T_(g)of less than or equal to about 30° C.
 29. The composition of claim 1,wherein a ratio of urethane structures to ester structures in thereaction product is at least 2:1.
 30. The composition of claim 1,wherein a ratio of urethane structures to ester structures in thereaction product is 4:1.
 31. The composition of claim 1, wherein thereaction product has a structure represented by one of: a.(material)-(polyisocyanate)-(material), b. (material)-(asymmetrical,saturated polyisocyanate)-(chain extension agent-asymmetrical, saturatedpolyisocyanate)m-(material), wherein m is any number that is at least 1and is based on an average of all reaction products, wherein carbamategroups of the material are terminal ends of the reaction product. 32.The composition of claim 1, wherein the reaction product has a numberaverage molecular weight of about 464 to about
 4000. 33. The compositionof claim 1 further comprising a polymer that is at least one of anacrylic, a vinyl, a polyurethane, a polycarbonate, a polyester, analkyd, and a polysiloxane.
 34. A method for forming the composition ofclaim 1 comprising reacting the asymmetrical, saturated polyisocyanate,the material, and optionally the chain extension agent.
 35. The methodof claim 34, wherein the reacting is one of a. reacting thepolyisocyanate, the chain extension agent, and the material together inone reaction, b. reacting the polyisocyanate with the chain extensionagent to form a reaction product A, and then reacting reaction product Awith the material, and c. reacting the material with the polyisocyanateto form a reaction product B, and then reacting reaction product B withthe chain extension agent.
 36. A coating composition comprising thecomposition of claim
 1. 37. The coating composition of claim 36 furthercomprising at least one of a crosslinker, a solvent, a catalyst, asurfactant, a filler, a stabilizer, a wetting agent, a dispersing agent,an adhesion promoter, a UV absorber, a hindered amine light stabilizer,a coloring agent, and an additional polymer.
 38. The coating compositionof claim 37 wherein the crosslinker is an aminoplast.
 39. A methodcomprising applying the coating composition of claim 36 to a substrate.40. A coating prepared from the coating composition of claim
 36. 41. Thecoating of claim 40, wherein the coating is at least one of a primer, abase coat, a top coat, a clearcoat, and a laminate.
 42. The coating ofclaim 40, wherein the coating has flex of from about 8 to about 10 asmeasured by General Motors GM9503P.
 43. The coating of claim 40, whereinthe coating has an etch of from about 2 to about 8 as measured byGeneral Motors World Specification GM W-3005 paragraph 5.15.